KR100293752B1 - Method for treating waste or waste plastic material - Google Patents

Abstract

PCT No. PCT/EP94/00954 Sec. 371 Date Dec. 27, 1995 Sec. 102(e) Date Dec. 27, 1995 PCT Filed Mar. 25, 1994 PCT Pub. No. WO94/22979 PCT Pub. Date Oct. 13, 1994A process is disclosed for processing used or waste plastic materials in order to recover chemical raw materials and liquid fuel components by depolymerisation of the used materials, which are transformed into a pumpable and into a volatile phase. The volatile phase is separated into a gaseous phase and a condensate or condensable depolymerisation product, which are refined by standard usual procedures. The pumpable phase remaining once the volatile phase is separated is subjected to liquid phase hydrogenation, gasification, low temperature carbonisation or to a combination of said processes.

Description

[Name of invention]

Method for treating waste or waste plastic material

Detailed description of the invention

The present invention relates to a method for treating waste or waste plastic material for the purpose of extracting chemical starting materials and liquid fuel components.

The present invention is based on a method for the hydrotreating of carbon-containing materials, whereby polymer waste, in particular in the form of ground or dissolved polymer wastes, is added to oils with high boiling points, and such mixtures are used to prepare fuel components and chemical starting materials. It is easy to hydrogenate in the presence of hydrogen for extraction (see DD 254 207 A1).

A method for converting used tires, rubber and / or other plastic materials into liquid, gaseous and solid products by depolymerization in a carrier under increased pressure and elevated temperature is described in DE-A-25 30 229. In particular, no hazardous substances such as sulfur dioxide, carbon black or the like reach the atmosphere. For example, after being crushed and mixed into recycle oil from a hydrogenated product, the used tire enters a hydrogenation reactor where hydrogen is added at a hydrogen pressure of 150 bar and a temperature of 450 ° C. in the presence of a substance that promotes decomposition and hydrogenation reactions.

DE-A-2 205 001 describes a method for the thermal treatment of waste material and unvulcanized rubber, whereby an auxiliary phase, which is variable in the reaction temperature of the waste material, is present at temperatures from 250 ° C. to 450 ° C. Decompose

In addition, in June 1974, Rubber Age, in consideration of the hydrogenation of used tires, with the aim of extracting carbon black, which can be reused as a hydrocarbon-based liquid product and filler material in the gas oil range. Ronald H. in Ronald H. Wolk, Michael C. Chervenak and Carmin A. Reference is made to pages 27 to 38 of the paper by Carmine A. Battista.

It is also known to dissolve polymer waste, in particular waste rubber, from residual oil from the treatment of crude oil. The resulting mixture is then subjected to a coking process for producing coke. In this way, gas and liquid products are obtained. In DD O 144 171, the latter is described as being able to be suitable as fuel components after proper treatment.

In the process according to DD 254 207, the polymer concentration in the hydrogenation starting product is for example between 0.01 and 20 mass%. The combined hydrogenation of heavy oils with dissolved or suspended polymers should be limited to the hydrogenation process where hydrogenation is carried out in a tube reactor with or without suspended catalyst. If the reactor was operated using a catalyst in a fixed bed, the use of the polymer would have been possible to a limited extent, especially when polymers already depolymerized were used, especially in the step of heating the polymer to about 420 ° C. before entering the reactor.

In this respect, the purpose in the method for treating waste plastic material is that it is not limited to the addition of up to 20 mass% of waste plastic material as a typical heavy oil conversion process in an oil refinery.

In the chemical conversion of waste products comprising plastics, another problem arises that the chlorine-containing plastic material must be processed simultaneously. Corrosive halide hydrides in the form of gaseous decomposition products during depolymerization according to the state of the technical process require special careful measurements.

The waste or waste plastic material partly contains a small amount of second inorganic components such as pigments, metals and fillers, which leads to other problems which lead to disadvantages in some depolymerization processes, for example reprocessing of depolymerized products. .

Accordingly, it is an object of the present invention to provide a method capable of withstanding such components. The components are of high quality at each stage, which can be sent to a reprocessing process, where other stages with which these components are tolerated while the second inorganic component is removed require less complex reprocessing procedures.

Other objects include that relief may be provided to complex and capital intensive process steps, such as low temperature carbonization, vaporization or liquid phase hydrogenation, or that the steps may be further utilized.

The present invention relates to a method for treating a waste or waste plastic material to extract chemical starting materials and liquid fuel components, wherein the starting material is depolymerized to produce a pumpable phase and a volatile phase, and the volatile phase The gas phase and condensate are separated and the condensable depolymerization product is subject to standard procedures common to oil refineries, and the pumped and remaining phase after separating the volatile phase is subjected to liquid phase hydrogenation, gasification, low temperature carbonization or a combination of the above process steps. Is dependent.

In the process, the resulting gas depolymerized product (gas), the resulting condensable depolymerized product (condensate) and the liquid phase (depolymer), which can be pumped and comprise a viscous depolymerized product, are separated into separate partial fluid streams. And the condensate and depolymerizer work alone. In this regard, it is preferred that the process parameters be chosen so that the maximum possible amount of condensate is produced.

Advantageous developments of the invention are also described in the dependent claims.

The plastic material used in this process is, for example, the mixing portion from the waste collection, among others, in particular by the Duale system German GmbH (DSD). The mixing portion includes, for example, polymer mixtures such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS and polycondensation products. Wastes from the production of plastic materials, commercial packaging waste of plastic materials, residues residues from the plastics processing industry, and mixed and unmixed pure portions may also be used, wherein the chemical composition of the plastic material wastes is intended for use in the present process. It is not critical to the criterion of conformity. Suitable starting materials also include elastomers, specialty rubber products, or waste tires in suitably ground form.

Waste and waste plastic materials are for example extracted from shaped parts, layered articles, composites, foils or sheets or from synthetic fibers. Examples of halogen-containing plastic materials are polyethylene chloride (PEC), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), chloroprene rubber, referred to only as a few important group members. Particularly in plastic materials containing sulfur, for example polysulphones or rubber crosslinked with sulfur bridges, if a suitable device is used to sort and classify first into plastic and metal components, such as in waste tires It is obtained in large quantities and is suitable for depolymerization and other processing to extract chemical starting materials or fuel components. In most processes the sulfidic sulfur obtained during this pretreatment step or chemical conversion process, which adds hydrogen, becomes waste gas and, as hydrogen chloride, the waste gas is separated and directed to another process.

Plastic synthetic materials, elastomers, and modified raw materials are included in the waste and waste plastic materials that can be used in the present process. In addition to the polymers described above, the modified raw materials are not only products based on cellulose, in particular pulses and paper, but also semi-finished products, individual parts, structural parts, packaging materials, as well as purchased items such as duroplastics and polyaddition compounds. Storage and transport containers. In addition, the semifinished product includes slabs, plates and substrates (printed circuit boards) as well as laminated sheets, which may partially contain a metal coating, and particles of 0.5 to 50 mm, if necessary, such as when other products are used, or After preliminary grinding to a partial size, it can be separated into metallic, glass or ceramic components by appropriate separation processes.

Generally, the wastes and waste plastics contain a second inorganic component such as pigment, glass fibers, fillers such as titanium oxide or zinc oxide, flame retardants, printing inks containing pigments, carbon black and metals such as for example aluminum elements. Include. The waste and waste plastic materials described above, which can be obtained, for example, from mixtures and batches of various components from the collection by DSD, may comprise up to 10 mass%, optionally up to 20 mass% of the second inorganic component. Can be. Such plastic material mixtures are generally used in the process, for example, as small particles or chips or the like, crushed or uniformly in a predetermined form.

The depolymerization process product is in principle a fluid flow of three main products.

1.) Fluid flow of the partial product sent to liquid hydrogenation, pressurization vaporization and / or low temperature carbonization (pyrolysis) between 15 and 85 mass% relative to the components and the mixture of plastic materials used according to their requirements. Can be divided into

What is involved here is a markedly heavy hydrocarbon with a break point greater than 480 ° C., which includes all inert materials introduced into the process by waste and waste plastic materials such as aluminum foils, pigments, fillers and glass fibers.

2.) Condensates, preferably in amounts of 10 to 80 mass% with respect to the mixture of plastic materials used, boil in the range between 25 ° C. and 250 ° C. and may contain up to about 1000 ppm of organic bound chlorine.

The condensate can be converted to high quality synthetic crude oil, for example by hydrotreating with a fixed bed commercial Co-Mo or Ni-Mo catalyst or it is a basic material containing hydrocarbon, which is a chemical technology process containing chlorine or It can be added directly to a typical oil refinery process.

3.) Gases in an amount of from about 5 to 20 mass% with respect to the mixture of plastic materials used may, in addition to methane, ethane, propane and butane, in principle contain gaseous halide hydrides such as hydrogen chloride and volatile hydrocarbon compounds.

Hydrogen chloride can be washed by, for example, water from the gas fluid stream to extract 30% aqueous hydrochloric acid. The residual gas may be freed of organic bound chlorine by liquid treatment or by hydrogenation in a hydrotreater and sent to, for example, a refinery gas treatment unit.

During other processes, individual product fluid streams, in particular condensates, can be adopted continuously in view of the recycling of the raw materials, for example as starting material for the production of olefins in ethylene plants.

An advantage of the process according to the invention is that the second inorganic components of the waste and waste plastics are of high quality in the liquid phase, while the condensates containing no such components are treated by a less complex process. In particular, it is possible to produce temperatures and high proportions of condensate and, on the other hand, to remain viscous depolymers from the liquid phase, which can be pumped under the control of the process. In this regard, a useful approach is that an increase at 10 ° C. temperature with an average residence time results in an increase of more than 50% in the yield of the product passing into the volatile phase. The dependence of the residence time with respect to two typical temperatures is shown in FIG.

It is also possible to optimize the yield of the condensate by addition of catalyst, stripping with water vapor, light boiling or other desirable features for hydrocarbon gas, turbulent agitation or pumping to the top.

A yield of about 50 mass% or more of condensate relative to the total amount of plastic material used in the depolymerization process is common for this process. Thus, it is advantageous to realize substantial cost savings in the costly process steps of pressurized vaporization, liquid phase hydrogenation and low temperature carbonization (pyrolysis).

The preferred temperature range for depolymerization for the process according to the invention is 150 to 470 ° C. Especially suitable range is 250-450 degreeC. The residence time can be 0.1 to 20 hours. A range of 1 hour to 10 hours is generally suitable. Pressure is an insignificant value in the process according to the invention. Thus, for example, when a volatile component is discharged for reasons related to the process, it is preferable to a process carried out in partial vacuum. Higher pressures require more equipment, but relatively high pressures are also possible. The pressure is generally in the range from 0.01 to 300 bar, in particular from 0.1 to 100 bar. The process is preferably carried out at an average pressure or slightly higher pressure, for example up to about 2 bar, which certainly reduces the costs associated with the apparatus. In order to completely degass the depolymer as much as possible and to increase the other condensate ratio, the process is advantageously carried out in a partial vacuum just about 0.2 apart.

The depolymerization can be carried out by adding a catalyst such as Lewis acid such as aluminum chloride, a substance forming a group such as hydrogen peroxide, or a zeolite containing a metal compound such as a heavy metal salt solution.

Depolymerization can also be carried out under turbulent conditions, for example by pumping the contents of the reactor with a mechanical stirrer. Another preferred embodiment of the process involves depolymerization under gas that is essentially inert with respect to inert gases, starting materials and depolymerization products such as N ₂ , CO ₂ , CO and hydrocarbons. In addition, the process may be carried out by injecting a stripping gas and stripping steam, such as nitrogen, water vapor and hydrocarbon gas.

In principle, it can be thought of as an advantage of a process that does not require the addition of hydrogen at this stage of the process.

Organic carriers used, ie carrier wastes, abandoned production batches of organic liquids, used oils and fractions from crude oil refining processes such as brittle residues are suitable as liquid auxiliary phases, ie carriers or carrier mixtures.

However, it is also possible to eliminate the addition of carrier or external oil and recycled internal oil.

The depolymerization process can be carried out in a conventional reactor, for example a vessel reactor of an agitator having an external circulation designed with corresponding process parameters such as pressure and temperature, the vessel material of which is an acid compound such as hydrogen chloride which can be formed. Withstands In particular, when depolymerization takes place with the addition of a catalyst, a "unit operation" process suitable for this purpose and used for the visbreaking of the residue from heavy oil or oil refining can be considered. This may be necessary for a facility to be adapted according to the requirements of the process according to the invention. The process step is advantageously designed for continuous operation, that is, the plastic material is continuously supplied to the liquid phase of the depolymerization reactor, and the depolymer and supernatant are continuously discharged.

Compared to the continuous reprocessing step of low temperature carbonization, liquid phase hydrogenation or vaporization, the costs associated with the apparatus are relatively low compared to the depolymerization process. In particular, this is correct when the process is carried out at normal pressure, ie in the range of 0.2 to 2 bar. Compared with the hydrogenation pretreatment, the costs associated with the device are significantly lower. In optimal control of the depolymerization process, the continuous process step can be reduced by 50% or more. High proportions of hydrocarbons that can be converted into valuable products by known and relatively simple processes are formed simultaneously during depolymerization.

After separating the gas and the condensate, the depolymer is simple to handle as it can be pumped and in this state is maintained to constitute a continuous process step and good filler.

In the present invention, the depolymer and the condensate are produced separately.

The condensable depolymerization product is preferably dependent on the hydrorefining process on a catalyst of particles of a fixed bed. Thus, the condensate can be subjected to conventional hydrogen treatment using commercial nickel / molybdenum or cobalt / molybdenum contacts, for example at partial hydrogen pressures of 10 to 250 bar and at temperatures of 200 to 430 ° C. In this respect, it is advantageous to provide a guide bed for blocking the entrained ash component or coke forming component depending on the component of the condensate obtained. As in the general case, the contacts can be arranged at the bottom of the solid and the fluid direction of the condensate can be provided in the direction of the head of the column being hydrotreated from the bottom or vice versa. In order to remove acid components such as halogen hydrides, hydrogen sulfide and the like, it would be advantageous if water, alkaline compounds and corrosion inhibitors were fed to the condensation section of a suitable separator.

The condensable depolymerization product or condensate is subjected to a hydrorefining process on a moving catalyst bed or in a fluid catalyst bed instead of the process being hydrotreated.

After passing through the hydrotreatment, the condensate resulting from the depolymerization is a good filler, for example for a steam fractionation unit.

For example, the liquid product obtained in the hydrotreater is further processed in ordinary refining plants as synthetic crude oil for obtaining fuel components or used in ethylene plants as chemical starting materials for producing ethylene, for example.

The gaseous components produced during the hydrotreating process are suitable, for example, for the addition of fillers for steam reforming.

In another preferred embodiment, the at least partial fluid flow of the depolymer is dependent on pressurization vaporization.

In principle, gas generators (Texaco, Shell, Prenflo) of all flowable beds, gas generators (Lurgi, Espag) and Ziwi gas generators of fixed beds are suitable for devices for pressurized gasification. In particular, the process is suitable for pyrolysis of hydrocarbons by oxygen, as is carried out in the combustion chamber in an oil vaporization process by partial oxidation of hydrocarbons in a flame reaction. The reaction is automatically thermoregulated without a catalyst.

Natural gas obtained during pressurized vaporization and comprising CO and H ₂ vatto can be used as synthesis gas or used to produce hydrogen.

In another preferred embodiment, the at least partial fluid flow of the depolymer is directed to a liquid phase hydrogenation process. Liquid phase hydrogenation is particularly preferred when a high proportion of liquid hydrocarbons are produced from the depolymer. For a description of the application of the liquid phase hydrogenation process for producing benzene and optionally for producing diesel oil from crude oil, reference is made to German Patent No. 933 826.

The liquid phase hydrogenation process of the liquid viscous depolymer in such a state so that it can be pumped is carried out such that, for example, if necessary, a pressure of 300 bar is mixed so that the mineral oil-rich brittle residue is mixed and a hydrogenation gas is added. For the purpose of preheating, the reactant material passes through a series of connected heat exchangers where heat exchange takes place with respect to the fluid flow of the product, for example the supernatant of the high temperature separator.

The reaction mixture, which is generally preheated to 400 ° C., is heated to the desired reaction temperature and then enters the reactor or reactor cascade in which the liquid phase hydrogenation process takes place.

In the high temperature separator connected at the bottom, the separation from the liquid and solid components of the gaseous components at the reaction temperature takes place under the pressure of the process. The liquid and solid components also include a second inorganic component.

The relatively heavy oil component may be separated into the gaseous portion in the separator in the first stage and expanded and then directed to an atmospheric distillation.

First, in the bottom separation system, the process gas is removed from the portion that has not condensed in the operation, and the process gas is recovered in the gas cleaning procedure and recycled as the system gas. For example, after other cooling, the residue of the hot separator product is removed from the process and directed to an atmospheric column for further reprocessing.

The liquid discharge from the hot separator is advantageously extended in two stages and is susceptible to vacuum distillation in order to separate any residual oil. In addition, the concentrated residue comprising the second inorganic component may be sent to the vaporization apparatus in liquid or solid form for the purpose of producing the synthesis gas.

In each case comprising the second inorganic component, the residue obtained in the liquid phase hydrogenation process (residue of the high temperature separator) and the low temperature carbonized coke obtained in the low temperature carbonization process of the depolymer can be used for other thermal process steps, where The residue obtained thereby and comprising the second inorganic component can be prepared for the purpose of recovering the metal.

The light oil and heavy oil fractions extracted from the liquid phase hydrogenation process can be used in general refineries as an important raw material for producing fuel or plastic material materials such as olefins and aromatics. If the product from the liquid phase hydrogenation process does not have stability of storage, it is dependent on the hydrogenation treatment provided in the process for condensate or condensable components.

A preferred embodiment of the process according to the invention is that the viscous depolymer in such a state so that it can be pumped is directed to the fluid flow of the portion to be directed to the pressurization vaporization operation and the flow product directed to the liquid phase hydrogenation process is condensed in the gaseous gas phase. Possible depolymerization products are classified after separation.

In the present invention, the separation into condensable components in the hydrotreatment step in such a state that it can be pumped, together with the pressurization vaporization and liquid hydrogenation processes and optionally the fractionation into partial fluid streams directed to pyrolysis, results in a significantly improved installation of the plant. Brings Utilization The apparatus has been developed for pressurized vaporization of solid fuels or for pyrolysis of hydrocarbons with oxygen, or in installations for the liquid phase hydrogenation of carbon containing materials under high pressure, which is a problem of capital intensive equipment components. Its processing capacity is optimally used when it is separated from the input material, i.e. the filler, which is previously separated by the fluid flow of condensate in the process and subject to separate reprocessing in the hydrotreating unit under the conditions of a relatively smooth process. .

Another preferred option of the present process is that the depolymerizer of at least one part of the fluid flow is subjected to low temperature carbonization gas, thereby extracting low temperature carbon gas, low temperature carbide and low temperature carbonized coke.

The condensable hydrogen chloride obtained in gaseous form or in the form of an aqueous solution during depolymerization can be directed to individual use in terms of the use of the material. The remaining portion, which is not a component of the depolymerization product, is passed in the gaseous state and is condensable in the yield of the liquid product and contains compounds containing organic chlorine compounds and sulfur and containing nitrogen are hetero atoms, chlorine, sulfur, nitrogen or even oxygen It is also removed and it is separated into hydrogen compounds in the liquid phase hydrogenation process or in the residue reprocessing process associated therewith.

Due to the high halogen content of the waste plastic material entering the process, it is advantageous to receive the gas depolymerization product discharged from the washing operation, in which the halogen hydrides formed in particular are separated in the form of water soluble halogen hydrogen acids and the utilization of the material Can be guided for.

The depolymerization product of the gas, in which acid components such as halogen hydride can be selectively removed, is preferably supplied as charged halogen gas or halogen system gas of the liquid phase hydrogenation process. The same applies to the low temperature carbonization gas which is separated during the low temperature carbonization.

As a result of the combination of depolymerization, preferably hydroprocessing, distillation (partial oxidation), and / or low temperature carbonization of the liquid depolymerization of the resultant distillation components, in terms of capacity, in particular technically difficult and complex but inorganic It is possible to reduce the following treatment steps to receive the components. The process according to the invention offers a high possibility for the recycling of filled plastic materials.

Thus, in a suitable combination of the above-described process steps, it is possible to achieve the use of a substantially complete material for the organic carbon contained in the plastic material entering the process. In most cases, it is possible for carbon chains or hydrocarbon chains to be included in the filled plastic waste to be obtained and for the material to be used. The remaining inorganic components can be shrouded for recycling, for example for the recycling of metals. It is also possible, at least in part, to use it again in its basic form as a catalyst in a liquid phase hydrogenation process.

The process according to the invention with the main plant parts of the depolymerization device, the hydrotreatment unit, the pressurized gasification unit, the liquid phase hydrogenation unit, the low temperature carbonization unit and the plant parts for reprocessing the gas depolymerization product is schematically illustrated in FIG. In FIG. 1, a plant arrangement comprising a low temperature carbonization unit is indicated by dashed lines as an optional plant component. The distribution of the combined material's fluid flow is shown schematically by the arrangement of the indicated feed lines. Reference numerals in FIG. 1 have the following meanings.

1. Depolymerization reactor

2. Hydrogenation Processor

3. Liquid Hydrogenation Unit

4. Gas unit

5. Low temperature carbonization plant

6. waste plastic materials

7. Short residue

8. Hydrochloric acid

9. Gases (methane, ethane, propane, hydrogen, etc.)

10. Condensate

11. Depolymer

12. Gases (methane, ethane, propane, H ₂ S, NH ₃ , H _2, etc.) (eg to steam reforming unit)

13. Synthetic crude oil Ⅱ (eg with olefin plant)

14. Syngas (CO / H ₂ )

15. Slag, carbon black (for example as a unit for reclaiming metal)

16. Gases (methane, ethane, propane, H ₂ S, NH ₃ , H _2, etc.) (eg to steam reforming unit)

17. Synthetic crude oil I (eg with refining unit)

18. Hydrogenation Residues (eg by gasification unit)

19. Gas (e.g. with liquid hydrogenation unit)

20. Tar (for example as a liquid hydrogenation unit)

21. Coke (eg with gasification unit)

A quantitative model for plant arrangement according to FIG. 1 is given in the following exemplary embodiment for the above filled material.

Waste plastic material, suitably crushed, optionally washed and dried, is continuously fed to the depolymerization reactor (1), the depolymerization reactor (1) having a device for heating, stirring and maintaining pressure, combined inlets and An outlet valve and a measurement and control device for controlling the level.

In a typical embodiment, with respect to the total reaction product, 50.0 mass% depolymer, 40.0 mass% condensate, 5.0 mass% gas hydrogen chloride and 5.0 mass% other gas are withdrawn. The condensate is directed to the hydrotreater 2, from which 35.0 mass% of synthetic crude oil and 5.0 mass% of gas reaction product are discharged to the top, the synthetic crude oil is fed to the olefin plant and the gas reaction product is steam reforming unit. Supplied by.

In the depolymer, 25 mass% enters the liquid hydrogenation unit 3 and the remaining 25 weight% enters the gasification unit 4. 25 mass% of brittle residue enters the liquid phase hydrogenation unit 3 as a recycle fluid stream. 10 mass% of gas reaction product entering the steam reforming unit, 40.0 mass% of synthetic crude oil entering the conventional refining plant and 5.0 mass% residue which can enter the gasification unit 4 are discharged. In a typical method of operation, the reaction product from the gasification unit comprises carbon black containing 24.0 mass% of synthesis gas and about 1.0 mass% of ash.

Alternatively, the product fluid flow of the depolymer from reactor 1 enters into a pyrolysis plant or a low temperature carbonization plant 5 to obtain partially pyrolysis coke, low temperature carbonized tar and low temperature carbonized gas. The pyrolysis coke enters the gasification unit and the low temperature carbonized tar and low temperature carbonized gas are directed to the liquid phase hydrogenation unit.

The second inorganic component concentrated in the depolymer is further concentrated by the next reprocessing. As the depolymer enters the gasification unit, the second inorganic component is consequently found in the discharged slag. In liquid phase hydrogenation, this is included in hydrogenation residues and low temperature carbonization in low temperature carbonized coke. If the hydrogenated residue and / or low temperature carbonized coke also enters the gasification unit, all the second inorganic components entering the process according to the invention are subjected to a reprocessing process in the form of gaseous slag.

2 shows a preferred design of the feed portion for waste and waste plastic material with a depolymerization plant comprising a reprocessing portion combined for gas and condensable depolymerization product. Reference numerals in FIG. 2 have the following meanings.

1. Silos for Waste Plastic Materials

2. Depolymerization reactor

3. furnace

4. Circulation pump

5. Suspension Pump

6. Filling container

7. High pressure pump

8. Condenser

9. Hydrochloric Acid Washer

10. Gas

11.fresh water

12. Water Soluble Hydrochloric Acid

13. Condensate (eg to hydrotreatment)

14. Fragile Remnants

15. Mixtures of depolymerizers / fragile residues (eg to liquid hydrogenation plants)

16. Means of transport

The waste and waste plastics reach the silo 1 via the conveying means 16 and then to the reactor 2. The reactor contents are heated by a circulation system comprising a circulation pump 4 and a furnace 3. From this circulation, the fluid flow is discharged via the suspension pump 5, and the fluid flow is mixed with the brittle residue in the filling container 6, which is supplied via the supply line 14 and then the high pressure pump 7 It is directed to other processing means via. The gas and condensable portion formed in the reactor 2 are separated towards the condenser 8. After passing through the hydrochloric acid scrubber 9, the washed gas 10 is directed to another location. The acid component previously included is removed after washing in the form of water-soluble hydrochloric acid (12). The condensate precipitated in the condenser 8 is directed from the condenser to another location.

Example 1

Depolymerization of Waste Plastic Materials

Mixed and agglomerated plastic material particles with an average particle diameter of 8 mm enter the continuous and pneumatically into the vessel reactor of the stirrer at a rate of 5 t / h, which has a capacity of 80 m 3 and a circulation system of 150 m 3 / h Is installed on. Mixed plastic materials are materials from domestic collection by the German Duale system and generally comprise 8% of PVC.

The plastic material mixture is depolymerized in the reactor at a temperature between 360 ° C and 420 ° C. By doing so, four parts are formed and their quantitative distribution is set in the following table as a coefficient of temperature of the reactor.

Ⅰ Ⅱ Ⅲ Ⅳ

T Gas Condensate Depolymerizer HCL

[° C] [mass%] [mass%] [mass%] [mass%]

360 4 13 81 2

380 8 27 62 3

400 11 39 46 4

420 13 47 36 4

The depolymerized polymer stream (III) is continuously discharged and directed to the liquid hydrogenation plant for other decomposition with a large number of (crusally) brittle residues in the mineral oil. The viscosity of the depolymer was 200 mPas at 175 ° C.

In a separate plant, the hydrocarbon condensate (fluid stream II) is condensed and directed for appropriate other treatments in the hydrotreater. Hydrogen chloride (fluid stream IV) in gaseous form is received by water and discharged as 30% aqueous hydrochloric acid. Hydrocarbon gas (fluid stream I) is directed to the liquid hydrogenation plant for conditioning.

Example 2

Desalination of Condensate

The condensate from the depolymerization plant obtained at a temperature between 400 and 420 ° C. from the plastic material mixture (DSD domestic collection) is HCl removed by washing with ammonia solution. Thus, it has a chlorine content of 400 ppm.

Thus, this condensate is dependent on the catalytic desalination process in a continuously operating apparatus. By doing so, as a first step the condensate is condensed at 50 bar and then hydrogen is sent to attach the gas / condensate at a rate of 1000 1 / kg. The mixture is heated and reacted on a NiMo catalyst by means of a fixed bed reactor. After passing through the reactor, the reaction mixture is cooled with ammonia water so that the hydrochloric acid formed is passed completely through the aqueous phase. Before expanding the reaction mixture, it is possible to expand the gas phase and the liquid phase, respectively, since gas phase / liquid phase separation takes place. After expansion, the liquid phase separates into an aqueous phase and an organic phase.

Regarding the amount, the organic phase expressed in an amount of more than 90 mass% of the condensate charged exhibits the following chlorine content [PPM] according to the selected reaction conditions.

Temperature [℃] WHSV [kg oil / kg catalyst / h]

0.5 1 2

370-<1 3

390 3 <1 <1

410 <1 <1

Under all reaction conditions, this grade of condensate meets the supply specifications of the crude oil refinery and is directed from the refinery to the upper distillation unit or to a special treatment plant (eg steam cracking plant).

Claims (10)

CLAIMS 1. A method for treating waste or waste plastic material to extract chemical starting material and liquid fuel components, the method comprising: depolymerizing the starting material to produce a pumpable phase and a volatile phase; The volatile phase is separated into a gas phase and a condensate, and the condensable depolymerization product is subject to the standard procedure common to oil refining equipment, and the phase remaining and pumped after separating the volatile phase is liquid hydrogenation, gasification, low temperature carbonization or the above procedure. Method dependent on the combination of steps. The depolymerization process according to claim 1, wherein the depolymerization process is carried out at a pressure of from 0.01 to 300 bar, preferably from 0.1 to 100 bar, in particular from 0.2 to 2 bar, from 150 to 470 ° C, preferably from 250 to 450 ° C and from 0.1 to 10h. , Preferably in each case relating to a plastic material mixture which is carried out at a residence time of 0.5 to 5 h and is subjected to the process, 1) 15 to 85.0 mass% of polymer, 2) 10.0 to 80.0 mass% of condensate and 3) a three-part fluid stream is withdrawn in an amount of 5.0 to 20.0 mass% gas mixture. The process according to claim 1 or 2, wherein the depolymerization process is carried out by addition of a catalyst. The method of claim 1 wherein the depolymerization process is performed under turbulent conditions. The method of claim 1 wherein the depolymerization process is performed under inert gas. The process according to claim 1, wherein the depolymerization process is carried out by application of a stripping medium such as nitrogen, water vapor, a gas containing hydrocarbons or other low boiling fractions. The method of claim 1 wherein the liquid auxiliary phase is added to the waste or waste plastics material introduced into the process. The process of claim 1, wherein the condensable depolymerization product is subject to a hydrorefining process on a catalyst of a fixed bed. The process of claim 1, wherein the condensable depolymerization product or condensate is subject to a hydrorefining process on a moving bed catalyst or on a fluidized bed catalyst. The method of claim 1, wherein the gas depolymerization product, which incorporates a washing procedure to remove acid components such as hydrogen chloride, enters the liquid phase hydrogenation process.